The invention relates to novel cationic 2-acylaminophenols of formula (I) comprising at least one cationic group, to their use as couplers for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, to oxidation dye compositions containing them in combination with at least one oxidation base, and to oxidation dyeing processes using them.
It is known practice to dye keratin fibres, and in particular human hair, with dye compositions containing oxidation dye precursors, in particular ortho-phenylenediamines, para-phenylenediamines, ortho-aminophenols or para-aminophenols and heterocyclic compounds such as diaminopyrazole derivatives, which are generally referred to as oxidation bases. The oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds which, when combined with oxidizing products, can give rise to coloured compounds and dyes by a process of oxidative condensation.
It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or coloration modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds.
The variety of molecules used as oxidation bases and couplers makes it possible to obtain a wide range of colours.
The so-called xe2x80x9cpermanentxe2x80x9d coloration obtained by means of these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must have no toxicological drawbacks and it must allow shades of the desired intensity to be obtained and have good resistance to external agents (light, bad weather, washing, permanent-waving, perspiration and friction).
The dyes must also allow white hairs to be covered, and, lastly, they must be as unselective as possible, i.e. they must allow the smallest possible differences in coloration to be produced over the entire length of the same keratin fibre, which may indeed be differently sensitized (i.e. damaged) between its tip and its root.
4-Aminophenol is generally used to obtain red shades, alone or as a mixture with other bases, and in combination with suitable couplers, and para-phenylenediamines are usually used to obtain blue shades. The use of meta-phenylenediamine-based couplers, in combination with para-phenylenediamine-based couplers usually leads to blue shades whose fastness is generally mediocre.
It has already been proposed, in particular in patent FR-A-1 596 879, to use, for the oxidation dyeing of keratin fibres, phenolic derivatives substituted in position 2 with a ureinyl or thioureinyl radical, in combination with para-phenylenediamine derivatives, in order to obtain shades close to those obtained with meta-phenylenediamine-based couplers. However, dye compositions containing the compounds cited in that patent generally lead on the hair to colours that are too selective and that lack intensity.
Moreover, it has already been proposed, in particular in patent BE 816 674, to use, for the dyeing of keratin fibres, in combination with para-phenylenediamine derivatives, phenolic derivatives substituted in position 2 with an acetyl or ureic radical and in position 5 with a halogen atom, in order to obtain dyeing results ranging from green to green-blue. The light-fastness of the shades obtained on the hair using these compositions are generally better than those obtained with dye compositions containing one or more meta-phenylenediamines as couplers. However, the fastness with respect to bad weather and washing, and the intensities of the colorations obtained are still too low and in these respects constitute major drawbacks for those skilled in the art.
In addition, it has already been proposed, in particular in patent application EP 0 579 204, to use, for the dyeing of keratin fibres, non-cationic phenolic derivatives substituted in position 2 with an acylamino, carbamoyl or ureyl radical, and in position 5 with a C1-C4 alkyl radical, in combination with para-phenylenediamine derivatives. However, the use of the phenolic derivatives cited in that European patent application does not make it possible to obtain a wide range of colours, and furthermore the blue shades generally obtained are not entirely satisfactory as regards their resistance to washing and to the action of light.
The Applicant has now discovered, entirely surprisingly and unexpectedly, that novel 2-acylaminophenols of formula (I) defined below comprising at least one cationic group of formula (II) defined below are not only suitable for use as couplers, but also make it possible to obtain dye compositions which give intense colorations with a wide range of colours, and having excellent properties of resistance with respect to the various treatments to which keratin fibres may be subjected.
These discoveries form the basis of the present invention.
A first subject of the invention is thus novel cationic 2-acylaminophenols of formula (I) below, and the addition salts thereof with an acid: 
in which:
the group A represents a group represented by the group D as defined below;
B1 and B2, independently of each other, represent a group represented by the group B as defined below;
k, l and m are integers which can take, independently of each other, the value 0 or 1; the sum k+l+m being non-zero;
W1 and W2 represent, independently of each other, a group W represented by formula (II) below: 
xe2x80x83in which formula (II):
R1 represents a hydrogen atom; a group Z as defined below; a linear or branched radical containing from 1 to 15 carbon atoms (it being possible for the branch(es) to form one or more 3- to 7-membered carbon-based rings) which can contain one or more double bonds and/or one or more triple bonds (the said double bonds optionally leading to aromatic groups), and one or more carbon atoms of which can be replaced with an oxygen, nitrogen or sulphur atom or with an SO2 group, and the carbon atoms of which can, independently of each other, be substituted with one or more halogen atoms; it being understood that the said SO2 group is not directly linked to the nitrogen atom in position 7 bearing the radical R1; the said radical R1 comprising no peroxide linkages or diazo, nitro or nitroso radicals; it being understood that the radical R1 does not represent a hydroxyl, amino, thio, alkoxy or alkylthio radical;
R2 represents a hydrogen atom; a group Z as defined below; a linear or branched radical containing from 1 to 20 carbon atoms (it being possible for the branch(es) to form one or more 3- to 7-membered carbon-based rings) which can contain one or more double bonds and/or one or more triple bonds (the said double bonds optionally leading to aromatic groups), and one or more carbon atoms of which can be replaced with an oxygen, nitrogen or sulphur atom or with an SO2 group, and the carbon atoms of which can, independently of each other, be substituted with one or more halogen atoms; the said radical R2 comprising no peroxide linkages or diazo, nitro or nitroso radicals; and it being understood that R2 cannot represent a hydroxyl or thio radical;
the radicals R1 and R2 can also be linked to form a saturated or unsaturated 5- to 7-membered ring consisting of carbon, nitrogen, oxygen, sulphur and/or of Cxe2x95x90O group, each ring member being unsubstituted or substituted with 1 or 2 radicals R, which may be identical or different, R being a linear or branched C1-C6 alkyl radical (it then being possible for the branch(es) to form one or more 3- to 6-membered rings), which can contain one or more double bonds and/or one or more triple bonds (the said double bonds possibly leading to aromatic groups), and one or more carbon atoms of which can be replaced with an oxygen, nitrogen or sulphur atom or with an SO2 group, and the carbon atoms of which can, independently of each other, be substituted with one or more halogen atoms; the said radical R comprising no peroxide linkages or diazo, nitro or nitroso radicals;
R3, R4 and R5, which may be identical or different, represent a hydrogen or halogen atom; a group Z as defined below; a linear or branched radical containing from 1 to 20 carbon atoms (it then being possible for the branch(es) to form one or more 3- to 7-membered rings) which can contain one or more double bonds and/or one or more triple bonds (the said double bonds optionally leading to aromatic groups), and one or more carbon atoms of which can be replaced with an oxygen, nitrogen or sulphur atom or with an SO2 group, and the carbon atoms of which can, independently of each other, be substituted with one or more halogen atoms; the said radicals R3, R4 and R5 comprising no peroxide linkages or diazo, nitro or nitroso radicals; and it being understood that Rs cannot represent a hydroxyl, thio or amino radical or a substituted or unsubstituted sulphonylamino group; and it being understood that the radicals R3, R4 and R5 cannot be linked to the benzene ring of formula (II) via an xe2x80x94NHxe2x80x94NHxe2x80x94 linkage;
the radicals R1 and R3 can also be linked to form a saturated 6- to 7-membered ring consisting of carbon, nitrogen, oxygen and sulphur and/or of Cxe2x95x90O group, each ring member being unsubstituted or substituted with 1 or 2 radicals R, which may be identical or different, R having the same meanings as those indicated above; the said radical R comprising no peroxide linkages or diazo, nitro or nitroso radicals;
the radicals R2 and R3 can also be linked to form a saturated 5- to 7-membered ring consisting of carbon, nitrogen, oxygen and sulphur and/or of Cxe2x95x90O group, each ring member being unsubstituted or substituted with 1 or 2 radicals R, which may be identical or different, R having the same meanings as those indicated above; the said radical R comprising no peroxide linkages or diazo, nitro or nitroso radicals;
Y represents a hydrogen or halogen atom; a group xe2x80x94OR6, xe2x80x94SR6 or xe2x80x94NHxe2x80x94SO2R6 in which R6 represents a linear or branched C1-C6 alkyl radical (it then being possible for the branch(es) to form one or more 3- to 6-membered rings) unsubstituted or substituted with one or more radicals chosen from the group consisting of a halogen atom, a hydroxyl, C1-C4 alkoxy, amino and C1-C4 aminoalkyl radical; a phenyl radical, unsubstituted or substituted with one or two radicals chosen from the group consisting of a C1-C4 alkyl, trifluoromethyl, carboxyl, (C1-C4)alkoxycarbonyl, halogen, hydroxyl, C1-C4 alkoxy, amino and C1-C4 aminoalkyl radical; or a benzyl radical; and it being understood that Y cannot represent xe2x80x94NHxe2x80x94SO2R6 when R3 represents a hydroxyl radical;
Z is a cationic group represented by formula (IV) below:
xe2x80x94(B)nDxe2x80x83xe2x80x83(IV)
xe2x80x83in which:
B represents a linear or branched radical containing from 1 to 15 carbon atoms (it then being possible for the branch(es) to form one or more 3- to 7-membered rings) which can contain one or more double bonds and/or one or more triple bonds, the said double bonds optionally leading to aromatic groups, and one or more carbon atoms of which can be replaced with an oxygen, nitrogen or sulphur atom or with an SO2 radical; and one or more carbon atoms of which can, independently of each other, be substituted with one or more halogen atoms or with one or more groups Z; the said radical B comprising no peroxide linkages and no diazo, nitro or nitroso radicals;
D is chosen from the cationic groups of formulae (V) and (VI) below: 
xe2x80x83in which:
the radical B is linked to the group D by any one of the atoms in the radical D;
n and p can, independently of each other, take the value 0 or 1;
when n=0, then the group of formula (VI) can be linked to the compound of formula (II) directly via the nitrogen atom of the quaternary ammonium, instead of the radical R10;
Z1, Z2, Z3 and Z4, independently of each other, represent an oxygen atom; a sulphur atom; a nitrogen atom which is unsubstituted or substituted with a radical R11; or a carbon atom which is unsubstituted or substituted with one or two radicals R11, which may be identical or different;
Z5 represents a nitrogen atom; or a carbon atom which is unsubstituted or substituted with a radical R11;
Z6 can take the same meanings as those indicated below for the radical R11, it being understood that Z6 is other than a hydrogen atom;
in addition, the radicals Z1 or Z5 can form, with Z6, a saturated or unsaturated 5- to 7-membered ring, each ring member being unsubstituted or substituted with one or two radicals R11, which may be identical or different;
R11 represents a hydrogen atom; a group Z; a linear or branched radical containing from 1 to 10 carbon atoms which can contain one or more double bonds and/or one or more triple bonds, it then being possible for the said double bonds optionally to lead to aromatic groups, and one or more carbon atoms of which can be replaced with an oxygen, nitrogen or sulphur atom or with an SO2 group, and one or more carbon atoms of which can, independently of each other, be substituted with one or more halogen atoms; the said radical comprising no peroxide linkages and no diazo, nitro or nitroso radicals;
two of the adjacent radicals Z1, Z2, Z3, Z4 and Z5 can also form a 5- to 7-membered ring, each ring member being independently represented by a carbon atom which is unsubstituted or substituted with one or two radicals R11, which may be identical or different; a nitrogen atom which is unsubstituted or substituted with a radical R11; an oxygen atom; or a sulphur atom;
R7, R8, R9 and R10, which may be identical or different, have the same meanings as those indicated above for the radical R11; the radicals R7, R8 and R9 can also form, in pairs with the quaternary nitrogen atom to which they are attached, one or more saturated 5- to 7-membered rings, each ring member being independently represented by a carbon atom which is unsubstituted or substituted with one or two radicals R11, which may be identical or different; a nitrogen atom which is unsubstituted or substituted with a radical R11; an oxygen atom; or a sulphur atom;
xxe2x88x92 represents an organic or inorganic anion and is preferably chosen from the group consisting of a halide group such as chloride, bromide, fluoride or iodide; a hydroxide; a sulphate; a hydrogen sulphate; a (C1-C6)alkyl sulphate such as, for example, a methyl sulphate or an ethyl sulphate; an acetate; a tartrate; an oxalate; a (C1-C6)alkyl sulphonate such as methyl sulphonate; an aryl sulphonate which is unsubstituted or substituted with a C1-C4 alkyl radical such as 4-tolyl sulphonate;
it being understood that:
the radical B1 is linked to the group A via any one of the atoms in the radical A;
when k=0, then the group A can be linked to the group W1 directly via the nitrogen atom of the quaternary ammonium, instead of the radical R10;
the radical B2 is linked to the group A via any one of the atoms in the radical A;
when m=0, then the group A of formula (VI) can be linked to the group W2 directly via the nitrogen atom of the quaternary ammonium, instead of the radical R10;
the group B1 of formula (I) is linked to an atom of the group W1 and this atom is identified by an asterisk (*) on the skeleton of W1 represented by formula (III) defined below;
the group B2 is linked to an atom of the group W2 and this atom is identified by an asterisk (*) on the skeleton of W2 represented by formula (III) defined below; 
when k+l=0, then W1 and/or W2 and/or B2 contain at least one group Z
when l+m=0, then W1 and/or W2 and/or B1 contain at least one group Z
when l=1, then k and m, independently of each other, can take the values 0 and 1.
As mentioned above, the oxidation dye composition containing the compound(s) of formula (I) in accordance with the invention makes it possible to obtain intense colorations in shades ranging from red to blue which furthermore have noteworthy fastness with respect to various treatments to which keratin fibres may be subjected. These properties are particularly noteworthy especially as regards the resistance of the colorations obtained with respect to the action of light, bad weather, washing, permanent-waving and perspiration.
According to the invention, when it is indicated that one or more of the carbon atoms of the radical(s) R1 to R5 can be replaced with an oxygen, nitrogen or sulphur atom or with an SO2 group, and/or when the said radicals R1 to R5 can contain one or more double bonds and/or one or more triple bonds, this means that it is possible, for example, to carry out the following conversions: 
According to the invention, R1 preferably denotes a hydrogen atom, a radical Z or a group A1, A2, A3, A4 or Asp optionally separated from the nitrogen located in position 7, to which the radical R1 is attached, by a xe2x80x94(CO)xe2x80x94 group.
According to the invention, the term xe2x80x9cgroup A1xe2x80x9d means a linear or branched C1-C alkyl radical, possibly bearing one or two double bonds or one triple bond, possibly being unsubstituted or substituted with a group chosen from a group A2, a group A4 and a group A5, possibly being unsubstituted or substituted with one or two groups, which may be identical or different, chosen from Nxe2x80x94(C1-C3)alkylamino, Nxe2x80x94(C1-C3)alkyl-Nxe2x80x94(C1-C3)alkylamino, (C1-C6)alkoxy, oxo, alkoxycarbonyl, acyloxy, amide, acylamino, ureyl, sulphoxy, sulphonyl, sulphonamido, sulphonylamino, bromo, cyano and carboxyl groups, and possibly being unsubstituted or substituted with one or more hydroxyl, fluoro or chloro groups.
The term xe2x80x9cgroup A2xe2x80x9d means an aromatic group such as phenyl or naphthyl, which may be unsubstituted or substituted with one to three groups, which may be identical or different, chosen from methyl, trifluoromethyl, ethyl, isopropyl, butyl, pentyl, fluoro, chloro, bromo, methoxy, trifluoromethoxy, ethoxy, propyloxy, acetyloxy, acetyl and cyano groups.
The term xe2x80x9cgroup A3xe2x80x9d means a heteroaromatic group chosen from furyl, thienyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, isothiazolyl, pyrazolyl, pyrazolotriazolyl, pyrazoloimidazolyl, pyrrolotriazolyl, pyrazolopyrimidyl, pyrazolopyridyl, pyridyl, pyrimidyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, indolyl, indolidinyl, isoindolyl, indazolyl, benzotriazolyl, quinolyl, benzimidazolyl and benzopyrimidyl groups, the said groups being unsubstituted or substituted with 1 to 3 radicals chosen from linear or branched C1-C4 alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, carboxyl, alkoxycarbonyl, halogen, amido, amino or hydroxyl radicals.
The term xe2x80x9cgroup A4xe2x80x9d means a C3-C7 cycloalkyl radical, a norbornanyl radical optionally bearing a double bond and unsubstituted or substituted with 1 or 2 radicals defined by linear or branched C1-C4 alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, carboxyl, alkoxycarbonyl, halogen, amido, amino and hydroxyl radicals.
The term xe2x80x9cgroup A5xe2x80x9d means a heterocycle chosen from dihydrofuryl, tetrahydrofuryl, butyrolactonyl, dihydrothienyl, tetrahydrothienyl, tetrahydrothienonyl, iminothiolane, dihydropyrrolyl, pyrrolidinyl, pyrrolidinonyl, imidazolidinonyl, imidazolidinothienyl, oxazolidinyl, oxazolidinonyl, oxazolanethione, thiazolidinyl, isothiazolonyl, mercaptothiazolinyl, pyrazolidinonyl, iminothiolane, dioxolanyl, pentalactone, dioxanyl, dihydropyridyl, piperidyl, pentalactam, morpholinyl, pyrazoli(di)nyl, pyrimi(di)nyl, pyrazinyl, piperazinyl and azepinyl.
Among these substituents, R1 preferably represents a hydrogen atom; a methyl, ethyl, isopropyl, allyl, phenyl, benzyl, fluorobenzyl, hydroxybenzyl, difluorobenzyl, trifluorobenzyl, chlorobenzyl, bromobenzyl, methoxybenzyl, dimethoxybenzyl, (trifluoromethoxy)benzyl, 3,4-methylenedioxybenzyl, 6-chloropiperonyl, 4-methylthiobenzyl, 4-methylsulphonylbenzyl, 4-acetylaminobenzyl, 4-carboxybenzyl, 1-naphthomethyl or 2-naphthomethyl radical; or a 2-hydroxyethyl, 2-methoxyethyl or 2-ethoxyethyl group.
Even more preferably, R1 represents a hydrogen atom or a methyl radical.
According to the invention, R2 preferably denotes a hydrogen atom or an amino group; a group Z; a group A1, A2, A3, A4 or A5 as defined above, optionally separated from the carbon (in position 8) of the amide function of the compound of formula (II) by an xe2x80x94Oxe2x80x94, xe2x80x94NH or xe2x80x94Nxe2x80x94(C1-C3)alkyl group.
Among these substituents, R2 preferably denotes a group Z; a radical chosen from the group (G1) consisting of a radical: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclopentylmethyl, 3-cyclopentylpropyl, cyclohexyl, 2-cyclohexylethyl, norbornan-2-yl, vinyl, 1-methylvinyl, 2-methylvinyl, 2,2-dimethylvinyl, allyl, 3-butenyl; phenyl, methylphenyl, dimethylphenyl, 2,4,6-trimethylphenyl, 4-ethylphenyl, (trifluoromethyl)-phenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, acetoxyphenyl, (trifluoromethoxy)phenyl, aminophenyl, 4-dimethylaminophenyl, fluorophenyl, difluorophenyl, fluoro(trifluoromethyl)phenyl, chlorophenyl, dichlorophenyl, bromophenyl, 1-naphthyl, 2-naphthyl, (2-methoxy)naphth-1-yl, benzyl, 4xe2x80x2-methoxybenzyl, 2xe2x80x2,5xe2x80x2-dimethoxybenzyl, 3,xe2x80x2,4xe2x80x2-dimethoxybenzyl, 4xe2x80x2-fluorobenzyl, 4xe2x80x2-chlorobenzyl, phenethyl, 2-phenylvinyl, (1-naphthyl)methyl, (2-naphthyl)methyl; tetrahydrofur-2-yl, fur-2-yl, 5-methyl-2-(trifluoromethyl)fur-3-yl, 2-methyl-5-phenylfur-3-yl, thien-2-yl, (thien-2-yl)methyl, 3-chlorothien-2-yl, 2,5-dichlorothien-3-yl, benzothien-2-yl, 3-chlorobenzothien-2-yl, isoxazol-5-yl, 5-methylisoxazol-3-yl, 3,5-dimethylisoxazol-4-yl, 1,3-dimethylpyrazol-5-yl, 1-ethyl-3-methylpyrazol-5-yl, 1-tertbutyl-3-methylpyrazol-5-yl, 3-tertbutyl-1-methylpyrazol-5-yl, 4-bromo-1-ethyl-3-methylpyrazol-5-yl, indol-3-ylcarboxyl, pyridyl, chloropyridyl, dichloropyridyl, 5-(bromo)pyrid-3-yl, piperazin-2-yl, quinoxal-2-yl; fluoromethyl, difluoromethyl, trifluoromethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, 1,1,2,2,3,3,4,4-octafluorobutyl, nonafluorobutyl, chloromethyl, chloroethyl, 1,1-dimethyl-2-chloroethyl, 1,2-dichloroethyl, 1-chloropropyl, 3-chloropropyl, 4-chlorobutyl, hydroxymethyl, methoxymethyl, phenoxymethyl, (4-chlorophenoxy)methyl, benzyloxymethyl, acetoxymethyl, 1,2-dihydroxyethyl, 1-phenoxyethyl, 1-acetoxyethyl, 2-(2-carboxyethoxy)ethyl, 1-phenoxyethyl, 1-acetoxyethyl, methoxycarbonyl, ethoxycarbonyl, (methoxycarbonyl)methyl, 2-carboxyethyl, 2-(methoxycarbonyl)ethyl, 2-carboxycyclopropyl, 2-carboxycyclohexane; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, neopentoxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, vinyloxy, allyloxy, propargyloxy, chloromethoxy, 1-chloroethoxy, 2-methoxyethoxy, 4-chlorobutoxy, phenoxy, 4-methylphenoxy, 4-fluorophenoxy, 4-bromophenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, naphth-2-yloxy, benzyloxy; amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, cyclohexylamino, allylamino, 2-chloroethylamino, 3-chloropropylamino, carboxymethylamino, phenylamino, fluorophenylamino, (trifluoromethyl)phenylamino, chlorophenylamino, bromophenylamino, 4-acetylphenylamino, methoxyphenylamino, (trifluoromethoxy)phenylamino, naphth-1-ylamino, benzylamino, phenethylamino, pyrid-3-ylamino, dimethylamino, 1-pyrrolidinyl, 4-morpholinyl.
When R1 and R2 form a ring, the said ring is referably chosen from 2-pyrrolidinon-1-yl, methyl-2-pyrrolidinon-1-yl, 5-carboxy-2-pyrrolidinon-1-yl, 5-methoxycarbonyl-2-pyrrolidinon-1-yl, pyrazolinon-1-yl, succinimid-1-yl, 3,5-diketopyrazolidin-1-yl, oxindolin-1-yl, maleimid-1-yl, isoindole-1,3-dion-2-yl, 2-piperidinon-1-yl and glutarimid-1-yl groups.
Even more preferably, R2 represents a radical chosen from the group (G2) consisting of a methyl, ethyl, propyl, allyl, phenyl, tetrahydrofur-2-yl, fur-2-yl, thien-2-yl, pyridyl, piperazin-2-yl, fluoromethyl, chloromethyl, 2-chloroethyl, methoxymethyl, acetoxymethyl, 1,2-dihydroxyethyl, methoxycarbonyl, 2-carboxyethyl, methoxy, ethoxy, propoxy, allyloxy, 2-chloroethoxy, 2-methoxyethoxy, amino, ethylamino, allylamino, 2-chloroethylamino, pyridylamino, dimethylamino, 1-pyrrolidinyl and 4-morpholinyl radical; or a group xe2x80x94D1, xe2x80x94Exe2x80x94D1, xe2x80x94Oxe2x80x94Exe2x80x94D1 or xe2x80x94NHxe2x80x94Exe2x80x94D1, in which xe2x80x94Exe2x80x94 represents a xe2x80x94(CH2)qxe2x80x94 arm, q being an integer equal to 1 or 2, and D1 represents a group Dxe2x80x2 chosen from 3-methylimidazolidinium-1-yl, 3-(2-hydroxyethyl)imidazolidinium-1-yl, 1,2,4-triazolinium-1-yl, 1,2,4-triazolinium-4-yl, Nxe2x80x94(C1-C4)alkylpyridinium-2-yl, Nxe2x80x94(Cl-C4)alkylpyridinium-3-yl, Nxe2x80x94(C1-C4)alkylpyridinium-4-yl, N-(2-hydroxyethyl)-pyridinium-2-yl, N-(2-hydroxyethyl)pyridinium-3-yl, N-(2-hydroxyethyl)pyridinium-4-yl, pyridinium-1-yl, tri(C1-C4)alkylammonium-N-yl, 1-methylpiperidinium-1-yl and 1,4-dimethylpiperazinium-1-yl groups.
Even more preferably, R2 represents a methyl, methoxymethyl, 2-carboxyethyl, methoxy, amino, ethylamino or 1-pyrrolidinyl radical; a group xe2x80x94D1, xe2x80x94Exe2x80x94D1, xe2x80x94Oxe2x80x94Exe2x80x94D1 or xe2x80x94NHxe2x80x94Exe2x80x94D1, in which xe2x80x94Exe2x80x94 represents a xe2x80x94(CH2)qxe2x80x94 arm, q=1 to 2, and D1 represents a group Dxe2x80x2 as defined above.
According to the invention, R3 and R4, which may be identical or different, preferably denote a hydrogen or halogen atom; a hydroxyl or amino group; a group Z; a group A1 as defined above; a group A1, A2, A3, A4 or A5 as defined above and separated from the phenolic nucleus of formula (II) by an oxygen atom or by an xe2x80x94NHxe2x80x94, xe2x80x94N(C1-C3)alkyl-, xe2x80x94NH(CO)xe2x80x94, xe2x80x94N(C2-C3)alkyl-COxe2x80x94, xe2x80x94NH[Cxe2x95x90NH]xe2x80x94, xe2x80x94NH(CO)NHxe2x80x94, xe2x80x94NH(CO)N(C1-C3)alkyl-, xe2x80x94NH(CO)Oxe2x80x94, xe2x80x94NHSO2xe2x80x94, xe2x80x94NHSO2NHxe2x80x94 or xe2x80x94NHSO2N(C1-C3)alkyl-group.
Among these substituents, R3 even more preferably represents a hydrogen or chlorine atom; a group Z; a methyl, hydroxymethyl, methoxymethyl, 1-hydroxyethyl, aminomethyl, methylaminomethyl, hydroxyl, methoxy, amino, methylamino or 2-hydroxyethylamino radical; a group xe2x80x94NH(CO)R12 in which R12 represents one of the radicals listed in the group (G1) as defined above; a group xe2x80x94NHSO2R13, in which R13 represents one of the radicals listed in the group (G3) consisting of methyl, trifluoromethyl, ethyl, 2-chloroethyl, propyl, 3-chloropropyl, isopropyl, butyl, thien-2-yl, hydroxyl, ethoxy and dimethylamino radicals.
When R1 and R3 form a ring, together with the nitrogen atom in position 7 of the compound of formula (II), the preferred linkage for xe2x80x94R1R3xe2x80x94 is xe2x80x94CH2CH2CH2xe2x80x94.
When R2 and R3 form a ring, together with the nitrogen atom in position 7 of the compound of formula (II), the preferred linkages for xe2x80x94R2R3xe2x80x94 are xe2x80x94CH2xe2x80x94, xe2x80x94C(CH3)2xe2x80x94 and xe2x80x94CH2CH2xe2x80x94.
Even more preferably, R3 represents a hydrogen atom; a methyl, hydroxymethyl, aminomethyl, hydroxyl, methoxy, amino or methylamino radical; a methanesulphonylamino group; an ethanesulphonylamino group; a dimethylaminosulphonylamino group; a group xe2x80x94NH(CO)R4 in which R14 represents one of the radicals listed in the group (G2) as defined above; or a group xe2x80x94Oxe2x80x94Exe2x80x94D2, xe2x80x94NHxe2x80x94Exe2x80x94D2, xe2x80x94NH(CO)xe2x80x94D2, xe2x80x94NH(CO)xe2x80x94Exe2x80x94D2, xe2x80x94NH(CO)Oxe2x80x94Exe2x80x94D2, xe2x80x94NH(CO)NHxe2x80x94Exe2x80x94D2, or xe2x80x94NH(SO2)xe2x80x94Exe2x80x94D2, in which xe2x80x94Exe2x80x94 has the same meaning as that indicated above and D2 represents a group Dxe2x80x2 as defined above.
Among these substituents, R4 preferably represents a hydrogen or chlorine atom; a group Z; a methyl, ethyl, hydroxymethyl, methoxymethyl, aminomethyl, methylaminomethyl, hydroxyl, methoxy, acetoxy, amino, methylamino, N-piperidino or N-morpholino radical; a group xe2x80x94NH(CO)R15 in which R15 represents one of the radicals listed in the group (G1) defined above; or a group xe2x80x94NHSO2R16 in which R16 represents one of the radicals listed in the group (G3) defined above.
Even more preferably, R4 represents a hydrogen or chlorine atom; a methyl, hydroxymethyl, aminomethyl, hydroxyl, methoxy, amino or methylamino radical; a methanesulphonylamino group; an ethanesulphonylamino group; a dimethylaminosulphonylamino group; a group xe2x80x94NH(CO)R17 in which R17 represents one of the radicals listed in the group (G2) defined above; or a group xe2x80x94Oxe2x80x94Exe2x80x94D3, xe2x80x94NHxe2x80x94Exe2x80x94D3, xe2x80x94NH(CO)xe2x80x94D3, xe2x80x94NH(CO)xe2x80x94Exe2x80x94D3, xe2x80x94NH(CO)Oxe2x80x94Exe2x80x94D3, xe2x80x94NH(CO)NHxe2x80x94Exe2x80x94D3 or xe2x80x94NH(SO2)xe2x80x94Exe2x80x94D3, in which xe2x80x94Exe2x80x94 has the same meaning as that given above, and D3 represents a group Dxe2x80x2 as defined above.
According to the invention, R5 is preferably chosen from a hydrogen or halogen atom; a group Z; a group A1 as defined above; a group A1, A2, A3, A4 or A5 as defined above and separated from the phenolic nucleus of the compounds of formula (II) by an oxygen or sulphur atom or by an xe2x80x94NHxe2x80x94, xe2x80x94N(C1-C3)alkyl-NH(CO)xe2x80x94, xe2x80x94N(C1-C3)alkyl(CO)xe2x80x94, xe2x80x94NH[Cxe2x95x90NH]xe2x80x94, xe2x80x94NH(CO)NHxe2x80x94, xe2x80x94NH(CO)N(C1-C3)alkyl- or xe2x80x94NH(CO)Oxe2x80x94 group.
Among these substituents, R5 preferably represents a hydrogen, chlorine, fluorine or bromine atom; a group Z; a methyl, trifluoromethyl, allyl, methoxy or methylamino radical; or a group xe2x80x94NH(CO)R18 in which R18 represents one of the radicals listed in the group (G1) defined above.
Even more preferably, R5 represents a hydrogen, chlorine or fluorine atom; a methyl, hydroxymethyl, aminomethyl, methoxy or methylamino radical; a group xe2x80x94NH(CO)R19 in which R19 represents one of the radicals listed in the group (G2) defined above; or a group xe2x80x94Oxe2x80x94Exe2x80x94D4, xe2x80x94NHxe2x80x94Exe2x80x94D4, xe2x80x94NH(CO)xe2x80x94D4, xe2x80x94NH(CO)xe2x80x94Exe2x80x94D4, xe2x80x94NH(CO)Oxe2x80x94Exe2x80x94D4 or xe2x80x94NH(CO)NHxe2x80x94Exe2x80x94D4, in which xe2x80x94Exe2x80x94 has the same meaning as that given above, and D4 represents a group Dxe2x80x2 as defined above.
According to the invention, Y is preferably chosen from a hydrogen, chlorine, fluorine or bromine atom; a methoxy, ethoxy, propoxy, benzyloxy or phenoxy group; or an xe2x80x94OCH2CH2OCH3, xe2x80x94OCH2CH2OCH3, xe2x80x94OCH2CH2N(CH3)2, xe2x80x94OCH2(CO)OH, xe2x80x94OCH2(CO)OCH3, xe2x80x94OCH2(CO)OC2H5, xe2x80x94SCH2CH2CO2H or xe2x80x94NHSO2CH3 group; it being understood that Y cannot represent an xe2x80x94NHSO2CH3 group when R3 represents a hydroxyl radical.
Even more preferably, Y represents a hydrogen or chlorine atom; or a methoxy, xe2x80x94OCH2(CO)OH or xe2x80x94OCH2(CO)OCH3 group.
Among the groups D which may be mentioned, for example, are imidazolinium, thiazolinium, oxazolinium, pyrrolinium, 1,2,3-triazolinium, 1,2,4-triazolinium, isoxazolinium, isothiazolinium, imidazolidinium, thiazolidinium, pyrazolinium, pyrazolidinium, oxazolidinium, pyrazoltriazolinium, pyrazoloimidazolinium, pyrrolotriazolinium, pyrazolopyrimidinium, pyrazolopyridinium, pyridinium, pyrimidinium, pyrazinium, triazinium, benzoimidazolinium, benzoxazolinium, benzothiazolinium, indolinium, indolidinium, isoindolinium, indazolinium, benzotriazolinium, quinolinium, tetrahydroquinolinium, benzoimidazolidinium, benzopyrimidinium, (C1-C4) tetraalkylammonium, polyhydroxy (C1-C4) tetraalkylammonium, dialkylpiperidinium, dialkylpyrrolidinium, dialkylmorpholinium, dialkylthiomorpholinium, dialkylpiperazinium, azepinium and 1,4-diazabicyclo[2,2,2]octanium groups.
Even more preferably, D represents a 3-methylimidazolidinium-1-yl, 3-(2-hydroxyethyl)imidazolidinium-1-yl, 1,2,4-triazolinium-1-yl, 1,2,4-triazolinium-4-yl, Nxe2x80x94(C1-C4)alkylpyridinium-2-yl, Nxe2x80x94(C1-C4)alkylpyridinium-3-yl, Nxe2x80x94(C1-C4)alkylpyridinium-4-yl, N-(2-hydroxyethyl)pyridinium-2-yl, N-(2-hydroxyethyl)pyridinium-3-yl, N-(2-hydroxyethyl)pyridinium-4-yl, pyridinium-1-yl, (C1-C4)trialkylammonium-N-yl, 1-methylpiperidinium-1-yl or 1,4-dimethylpiperazinium-1-yl group.
A preferably represents an imidazolidinium, Nxe2x80x94(C1-C4)alkylpyridinium, N-(2-hydroxyethyl)pyridinium, pyridinium, di(C1-C4)alkylammonium or 1,4-dimethylpiperazinium-1-yl group.
Preferably, B, B1 and B2, independently of each other, represent a xe2x80x94(CH2)xe2x80x94, xe2x80x94(CH2)xe2x80x94(CH2)xe2x80x94 or xe2x80x94(CH2)xe2x80x94(CH2)xe2x80x94(CH2)xe2x80x94 arm.
Among the compounds of formula (I) above which may be mentioned most particularly are:
1,3-bis[(2-hydroxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-methylphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-aminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-acetylaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-methoxycarbonylaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(3-hydroxy-4-acetylaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(3-hydroxy-4-methoxycarbonylaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-5-chlorophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-methyl-5-chlorophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-amino-5-chlorophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-acetylamino-5-chlorophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-methoxycarbonylamino-5-chlorophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(3-hydroxy-4-acetylamino-5-chlorophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(3-hydroxy-4-methoxycarbonylamino-6-chlorophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-5-methoxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-methyl-5-methoxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-amino-5-methoxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-acetylamino-5-methoxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-methoxycarbonylamino-5-methoxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(3-hydroxy-4-acetylamino-6-methoxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(3-hydroxy-4-methoxycarbonylamino-6-methoxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-6-aminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-6-acetylaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4,6-diaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-4-acetylamino-6-aminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-3,5-dichloro-4-methylphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-3,5-dichloro-4-aminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-3,5-dichloro-4-acetylaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-3,5-dichloro-4-methoxycarbonylaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,3-bis[(2-hydroxy-3-acetylaminophenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
3-[(2-hydroxy-4-aminophenylcarbamoyl)methyl]-1-[(2-hydroxy-4-methylphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
3-[(2-hydroxy-3,5-dichloro-4-methylphenylcarbamoyl)methyl]-1-[(2-hydroxy-4-methylphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1,4-bis[(2-hydroxyphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-methylphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-aminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-acetylaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-methoxycarbonylaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(3-hydroxy-4-acetylaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(3-hydroxy-4-methoxycarbonylaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-5-chlorophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-methyl-5-chlorophenylcarbamoyl)methyl]-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-amino-5-chlorophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-acetylamino-5-chlorophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-methoxycarbonylamino-5-chlorophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(3-hydroxy-4-acetylamino-6-chlorophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(3-hydroxy-4-methoxycarbonylamino-6-chlorophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-5-methoxyphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-methyl-5-methoxyphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-amino-5-methoxyphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-acetylamino-5-methoxyphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-methoxycarbonylamino-5-methoxyphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(3-hydroxy-4-acetylamino-6-methoxyphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(3-hydroxy-4-methoxycarbonylamino-6-methoxyphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-6-aminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-6-acetylaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4,6-diaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-4-acetylamino-6-aminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-3,5-dichloro-4-methylphenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-3,5-dichloro-4-aminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-3,5-dichloro-4-acetylaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-3,5-dichloro-4-methoxycarbonylaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
1,4-bis[(2-hydroxy-3-acetylaminophenylcarbamoyl)methyl]-1-methylpiperazin-1-ium chloride;
and the addition salts thereof with an acid.
The compounds of formula (I) in accordance with the invention can be prepared according to methods that are well known in the prior art and are described, for example, in patents and patent applications FR-A-1 596 879; BE 816 674; EP 0 579 204; DE 2 846 931; JP-54-115 230; GB 2 070 000; DE 3 027 128; EP 0 065 874; EP 0 115 194; EP 0 079 141; EP 0 081 321; DE 3 246 238; EP 0 168 729; DE 3 414 051; JP-59-059 656; FR-A-2 575 470; EP 0 193 051; JP-63-208 562; JP-62-173 469; JP-62-108 859; JP-62-173 469; DD 253 997; DE 3 641 825, JP-63-208 562; DE 3 621 215; JP-01-249 739; JP-64-002 045; JP-02-255 674; JP-01-032 261; JP-02-255 674; EP 0 608 896; WO 94/19316; JP-09-169 705; EP 0 790 240; as well as in the documents Res. Discl. (1981), 202, 76-8; Synthesis (1982), 940-2; Res. Discl. (1983), 235, 352-3; Res. Discl. (1984), 247, 554-6, Res. Discl. (1985), 251, 134-9; Chem. Ind. (Dekker) (1992), 47 (Catal. Org. React.), 147-51; and J. Med. Chem. (1998), 41, 4062-79.
Another subject of the invention is the use of the compounds of formula (I) in accordance with the invention as couplers for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
The invention also relates to a composition for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, characterized in that it comprises, in a medium which is suitable for dyeing, at least one compound of formula (I) in accordance with the invention and at least one oxidation base.
The compound(s) of formula (I) in accordance with the invention and/or the addition salt(s) thereof with an acid preferably represent(s) from 0.0005 to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately relative to this weight.
The nature of the oxidation base(s) which can be used in the dye composition in accordance with the invention is not critical. They are preferably chosen from the oxidation bases conventionally used in oxidation dyeing, among which mention may be made in particular of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the para-phenylenediamines which can be mentioned more particularly, for example, are para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-chloroaniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(O-hydroxyethyl)-para-phenylenediamine, N-(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine and N-(xcex2-methoxyethyl)-para-phenylenediamine, and the addition salts thereof with an acid.
Among the para-phenylenediamines mentioned above, the ones most particularly preferred are para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl -para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 2,-chloro-para-phenylenediamine and 2-xcex2-acetylaminoethyl oxy-para-phenylenediamine, and the addition salts thereof with an acid.
Among the bis(phenyl)alkylenediamines which can be mentioned more particularly, for example, are N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)-tetramethylenediamine, N,Nxe2x80x2-bis(P-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)-ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition salts thereof with an acid.
Among the para-aminophenols which can be mentioned more particularly, for example, are para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.
Among the ortho-aminophenols which can be mentioned more particularly, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.
Among the heterocyclic bases which can be mentioned more particularly, for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Among the pyridine derivatives which may be mentioned more particularly are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(xcex2-methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine, and the addition salts thereof with an acid.
Among the pyrimidine derivatives which may be mentioned more particularly are the compounds described, for example, in German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[1,5-a]pyrimidin-7-ol, 3-aminopyrazolo[1,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl) (2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine and 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, and the addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists, and the addition salts thereof with an acid.
Among the pyrazole derivatives which may be mentioned more particularly are the compounds described in patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(xcex2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4xe2x80x2-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2xe2x80x2aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(xcex2-hydroxyethyl)amino-1-methylpyrazole, and the addition salts thereof with an acid.
According to the invention, the dye compositions containing one or more para-phenylenediamines and/or one or more heterocyclic oxidation bases are particularly preferred.
The oxidation base(s) preferably represent(s) from 0.0005% to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005% to 6% by weight approximately relative to this weight.
In addition to the compound(s) of formula (I) above, the dye composition in accordance with the invention can also include one or more additional couplers which can be chosen from the couplers used conventionally in oxidation dyeing and among which mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indolene derivatives, pyridine derivatives and pyrazolones, and the addition salts thereof with an acid.
These couplers are chosen more particularly from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazol-5-one, and the addition salts thereof with an acid.
When they are present, these couplers preferably represent from 0.0001 to 10% by weight approximately relative to the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately relative to this weight.
In general, the addition salts with an acid which can be used in the context of the dye compositions of the invention (compounds of formula (I), additional oxidation bases and couplers) are chosen in particular from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The medium which is suitable for dyeing (or the support) generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in water. As organic solvent, mention may be made, for example, of C1-C4 lower alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof.
The solvents can be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
The pH of the dye composition in accordance with the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value using acidifying or basifying agents commonly used to dye keratin fibres.
Among the acidifying agents which may be mentioned, for example, are inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.
Among the basifying agents which may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (V) below: 
in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; R23, R24, R25 and R26, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical.
The oxidation dye compositions in accordance with the invention can also include at least one direct dye, in particular in order to modify the shades or to enrich them with glints.
The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, packaging agents such as, for example, silicones, which may or may not be volatile or modified, film-forming agents, ceramides, preserving agents and opacifiers.
Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the addition(s) envisaged.
The dye composition according to the invention can be in various forms, such as in the form of liquids, creams or gels or in any other form which is suitable for dyeing keratin fibres, and in particular human hair.
The invention also relates to a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, using the dye composition as defined above.
According to this process, at least one dye composition as defined above is applied to the fibres, the colour being developed at acidic, neutral or alkaline pH using an oxidizing agent which is added to the dye composition just at the time of use, or which is present in an oxidizing composition which is applied simultaneously or sequentially.
According to one preferred embodiment of the dyeing process of the invention, the dye composition described above is preferably mixed, at the time of use, with an oxidizing composition containing, in a medium which is suitable for dyeing, at least one oxidizing agent present in an amount which is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres and is left in place for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which the fibres are rinsed, washed with shampoo, rinsed again and dried.
The oxidizing agent can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibres, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes such as peroxidases, laccases, tyrosinases and oxidoreductases among which mention may be made in particular of pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases.
The pH of the oxidizing composition containing the oxidizing agent as defined above is such that, after mixing with the dye composition, the pH of the resultant composition applied to the keratin fibres preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It is adjusted to the desired value using acidifying or basifying agents commonly used to dye keratin fibres and as defined above.
The oxidizing composition as defined above can also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
The composition which is finally applied to the keratin fibres can be in various forms, such as in the form of liquids, creams, gels or any other form which is suitable for dyeing keratin fibres, and in particular human hair.
Another subject of the invention is a multi-compartment dyeing device or xe2x80x9ckitxe2x80x9d or any other multi-compartment packaging system, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition as defined above. These devices can be equipped with a means for delivering the desired mixture onto the hair, such as the devices described in patent FR 2,586,913 in the name of the Applicant.